Emulsion dyeing composition containing at least one fatty quaternary amine, at least one nonionic surfactant and at least one silicone, and method of using same

ABSTRACT

The present invention is drawn to a composition and method for coloring keratinous substrates containing: (a) at least one fatty quaternary amine; (b) at least one nonionic surfactant; (c) at least anionic silicone; (d) at least one dye chosen from oxidation dye precursors and direct dyes; (e) optionally, at least one thickening agent; (f) optionally, at least one alkaline agent; (g) optionally, at least one fatty substance other than a fatty acid; (h) optionally, at least one salt; and (i) optionally, at least one oxidizing agent.

STATEMENT OF RELATED APPLICATIONS

Not applicable.

BACKGROUND OF THE INVENTION

Throughout the years, people have sought to modify the color of theirskin, their eyelashes or their hair. Several techniques have beendeveloped to achieve the desired color.

It is known to dye human keratinous substrates, such as the hair, withdye compositions comprising oxidation dye precursors, which are alsoknown as oxidation bases. To vary the shades obtained with theseoxidation bases, additional couplers or coloration modifiers may beemployed.

It is also known to dye human keratinous substrates by direct dyeing,which comprises applying to the keratinous substrates direct dyes, whichare colored.

Traditional application time for dyeing keratinous substrates is aroundthirty minutes. Such a period is considered to be too long under currenttendency.

This problem cannot be solved by merely reducing the application time ofthe dyeing compositions since it would be difficult to maintain the samesatisfactory levels of coloring in shortened application times.

Another way to solve the problem is to increase the power of theoxidizing agent and the alkaline agent, by employing, for example,oxidizing agents of the type of the persalts, and/or alternatively byincreasing the pH of the dyeing composition. However, such an option isundesirable, because of the increased risk of degradation of thekeratinous substrates.

Therefore, there is a real need to develop dyeing compositions withimproved efficiency to yield minimum degradation of the treatedkeratinous substrates while achieving improved levels of coloring inboth conventional application time e.g., around 30 minutes and inshortened application times, e.g., around 15 minutes.

Another object of the present invention is to provide an effectivedyeing composition capable of depositing acceptable levels of color ontokeratinous substrates utilizing decreased levels of dye therein.

It is also desirable that such a composition can provide otheradvantageous properties to the hair such as shine, conditioning and ahealthy appearance. Finally, it is an object of the present invention toprovide an effective dyeing composition with lowered cost of production.

BRIEF SUMMARY OF THE INVENTION

The present invention is directed to a ready-to-use aqueous compositionfor dyeing keratinous substrates containing, in a cosmeticallyacceptable medium:

-   -   a) at least one fatty quaternary amine compound;    -   b) at least one nonionic surfactant;    -   c) at least one anionic silicone;    -   d) at least one dye chosen from oxidation dye precursors and        direct dyes;    -   e) optionally, at least one thickening agent;    -   f) optionally, at least one alkaline agent;    -   g) optionally, at least one fatty substance other than a fatty        acid;    -   h) optionally, at least one salt; and    -   i) optionally, at least one oxidizing agent.

The present invention is also drawn to a method of dyeing keratinoussubstrates, comprising applying onto the keratinous substrates aready-to-use aqueous composition containing, in a cosmeticallyacceptable medium:

-   -   a) at least one fatty quaternary amine compound;    -   b) at least one nonionic surfactant;    -   c) at least one anionic silicone;    -   d) at least one dye chosen from oxidation dye precursors and        direct dyes;    -   e) optionally, at least one thickening agent;    -   f) optionally, at least one alkaline agent;    -   g) optionally, at least one fatty substance other than a fatty        acid;    -   h) optionally, at least one salt; and    -   i) optionally, at least one oxidizing agent.

According to another embodiment of the invention, a kit for dyeingkeratinous substrates is provided, comprising:

a first unit containing in a cosmetically acceptable medium: at leastone fatty quaternary amine compound; at least one nonionic surfactant;at least one phosphate ester chosen from alkoxylated alkyl phosphateesters and alkyl phosphate esters; and at least one dye chosen fromoxidation dye precursors and direct dyes; optionally, at least onethickening agent; optionally, at least one alkaline agent; optionally,at least one fatty substance other than a fatty acid; and optionally, atleast one salt; and

a second unit comprising at least one oxidizing agent and optionally, atleast one fatty substance other than a fatty acid.

DETAILED DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients and/or reaction conditionsare to be understood as being modified in all instances by the term“about” which encompasses ±10%.

“Amino groups” as defined herein includes primary amino groups,secondary amino groups, and tertiary amino groups, and further includesamino groups which are terminal, pendant, and intercalated in a skeletonof the at least one polyamine compound, but does not, for example,include quaternary amino groups, amido groups, imino groups, nitrilogroups, or heteroatom analogs of any of the foregoing.

“At least one” as used herein means one or more and thus includesindividual components as well as mixtures/combinations.

“Conditioning” as used herein means imparting to at least one keratinousfiber at least one property chosen from combability, manageability,moisture-retentivity, luster, shine, and softness. The state ofconditioning is evaluated by measuring, and comparing, the ease ofcombability of the treated hair and of the untreated hair in terms ofcombing work (gm-in).

“Formed from,” as used herein, means obtained from chemical reaction of,wherein “chemical reaction,” includes spontaneous chemical reactions andinduced chemical reactions. As used herein, the phrase “formed from”, isopen ended and does not limit the components of the composition to thoselisted, e.g., as component (i) and component (ii). Furthermore, thephrase “formed from” does not limit the order of adding components tothe composition or require that the listed components (e.g., components(i) and (ii)) be added to the composition before any other components.

“Hydrocarbons,” as used herein, include alkanes, alkenes, and alkynes,wherein the alkanes comprise at least one carbon, and the alkenes andalkynes each comprise at least two carbons; further wherein thehydrocarbons may be chosen from linear hydrocarbons, branchedhydrocarbons, and cyclic hydrocarbons; further wherein the hydrocarbonsmay optionally be substituted; and further wherein the hydrocarbons mayoptionally further comprise at least one heteroatom intercalated in thehydrocarbon chain.

“Silicone compound,” as used herein, includes, for example, silica,silanes, silazanes, siloxanes, and organosiloxanes; and refers to acompound comprising at least one silicon; wherein the silicone compoundmay be chosen from linear silicone compounds, branched siliconecompounds, and cyclic silicone compounds; further wherein the siliconecompound may optionally be substituted; and further wherein the siliconecompound may optionally further comprise at least one heteroatomintercalated in the silicone chain, wherein the at least one heteroatomis different from the at least one silicon.

“Substituted,” as used herein, means comprising at least onesubstituent. Non-limiting examples of substituents include atoms, suchas oxygen atoms and nitrogen atoms, as well as functional groups, suchas hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups,oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups,amine groups, acylamino groups, amide groups, halogen containing groups,ester groups, thiol groups, sulphonate groups, thiosulphate groups,siloxane groups, and polysiloxane groups. The substituent(s) may befurther substituted.

“Ethylene oxide group” as defined herein refers to a group of formula—CH₂CH₂—O—.

“Propylene oxide group” as defined herein includes groups of formula—CH₂CH₂CH₂—O—, groups of formula (CH₃)CHCH₂—O—, and groups of formula—CH₂(CH₃)CH—O—.

“Keratinous substrate” may be chosen from, for example, hair, eyelashes,and eyebrows, as well as the stratum corneum of the skin and nails.

“Polymers,” as defined herein, include homopolymers and copolymersformed from at least two different types of monomers.

The present invention provides for the use of conventional fattyquaternary amine compounds containing from about 6 to about 22 carbonatoms. The anion of the quaternary ammonium compound can be a common ionsuch as chloride, ethosulfate, methosulfate, acetate, bromide, lactate,nitrate, phosphate, or tosylate and mixtures thereof. The long chainalkyl groups can include additional or replaced carbon or hydrogen atomsor ether linkages. Other substitutions on the quaternary nitrogen can behydrogen, benzyl or short chain alkyl or hydroxyalkyl groups such asmethyl, ethyl, hydroxymethyl or hydroxyethyl, hydroxypropyl orcombinations thereof.

Examples of fatty quaternary ammonium compounds include but are notlimited to: Behentrimonium chloride, Cocotrimonium chloride,Cethethyldimonium bromide, Dibehenyldimonium chloride, Dihydrogenatedtallow benzylmonium chloride, disoyadimonium chloride, Ditallowedimoniumchloride, Hydroxycetyl hydroxyethyl dimonium chloride, HydroxyethylBehenamidopropyl dimonium chloride, Hydroxyethyl Cetyldimonium chloride,Hydroxyethyl tallowedimonium chloride, myristalkonium chloride, PEG-2Oleamonium chloride, PEG-5 Stearmonium chloride, PEG-15 cocoylquaternium 4, PEG-2 stearalkonium 4, lauryltrimonium chloride;Quaternium-16; Quaternium-18, lauralkonium chloride, olealkoniumchloride, cetylpyridinium chloride, Polyquaternium-5, Polyquaternium-6,Polyquaternium-7, Polyquaternium-10, Polyquaternium-22,Polyquaternium-37, Polyquaternium-39, Polyquaternium-47, cetyl trimoniumchloride, dilauryldimonium chloride, cetalkonium chloride,dicetyldimonium chloride, soyatrimonium chloride, stearyl octyl dimoniummethosulfate, behentrimonium methosulfate (18-MEA), stearalkoniumchloride, and mixtures thereof. Other quaternary ammonium compounds arelisted in the CTFA Cosmetic Ingredient Handbook, First Edition, on pages41-42, incorporated herein by reference.

In the present invention, the at least one fatty quaternary aminecompound is preferably used in an amount of from greater than 0% toabout 30% by weight, preferably from about 0.1% to about 20% by weight,and more preferably from about 1% to about 10%, or from about 2% toabout 5% by weight, based on the weight of the composition as a whole.

Nonionic Surfactants

In general, nonionic surfactants having a Hydrophilic-Lipophilic Balance(HLB) of from 8 to 20, are contemplated for use by the presentinvention. Nonlimiting examples of nonionic surfactants useful in thecompositions of the present invention are disclosed in McCutcheon's“Detergents and Emulsifiers,” North American Edition (1986), publishedby Allured Publishing Corporation; and McCutcheon's “FunctionalMaterials,” North American Edition (1992); both of which areincorporated by reference herein in their entirety.

Examples of nonionic surfactants useful herein include, but are notlimited to, alkoxylated derivatives of the following: fatty alcohols,alkyl phenols, fatty acids, fatty acid esters and fatty acid amides,wherein the alkyl chain is in the C₁₂-C₅₀ range, preferably in theC₁₆-C₄0 range, more preferably in the C₂₄ to C₄₀ range, and having fromabout 1 to about 110 alkoxy groups. The alkoxy groups are selected fromthe group consisting of C₂-C₆ oxides and their mixtures, with ethyleneoxide, propylene oxide, and their mixtures being the preferredalkoxides. The alkyl chain may be linear, branched, saturated, orunsaturated. Of these alkoxylated non-ionic surfactants, the alkoxylatedalcohols are preferred, and the ethoxylated alcohols and propoxylatedalcohols are more preferred. The alkoxylated alcohols may be used aloneor in mixtures thereof. The alkoxylated alcohols may also be used inmixtures with those alkoxylated materials disclosed herein-above.

Other representative examples of such ethoxylated fatty alcohols includelaureth-3 (a lauryl ethoxylate having an average degree of ethoxylationof 3), laureth-23 (a lauryl ethoxylate having an average degree ofethoxylation of 23), ceteth-10 (a cetyl alcohol ethoxylate having anaverage degree of ethoxylation of 10) steareth-10 (a stearyl alcoholethoxylate having an average degree of ethoxylation of 10), andsteareth-2 (a stearyl alcohol ethoxylate having an average degree ofethoxylation of 2), steareth-100 (a stearyl alcohol ethoxylate having anaverage degree of ethoxylation of 100), beheneth-5 (a behenyl alcoholethoxylate having an average degree of ethoxylation of 5), beheneth-10(a behenyl alcohol ethoxylate having an average degree of ethoxylationof 10), and other derivatives and mixtures of the preceding.

Also available commercially are Brij® nonionic surfactants from Uniqema,Wilmington, Del. Typically, Brij® is the condensation products ofaliphatic alcohols with from about 1 to about 54 moles of ethyleneoxide, the alkyl chain of the alcohol being typically a linear chain andhaving from about 8 to about 22 carbon atoms, for example, Brij 72(i.e., Steareth-2) and Brij 76 (i.e., Steareth-10).

Also useful herein as nonionic surfactants are alkyl glycosides, whichare the condensation products of long chain alcohols, e.g. C₈ to C₃₀alcohols, with sugar or starch polymers. These compounds can berepresented by the formula (S)_(n)—O—R wherein S is a sugar moiety suchas glucose, fructose, mannose, galactose, and the like; n is an integerof from about 1 to about 1000, and R is a C₈ to C₃₀ alkyl group.Examples of long chain alcohols from which the alkyl group can bederived include decyl alcohol, cetyl alcohol, stearyl alcohol, laurylalcohol, myristyl alcohol, oleyl alcohol, and the like. Preferredexamples of these surfactants are alkyl polyglucosides wherein S is aglucose moiety, R is a C₈ to C₂₀ alkyl group, and n is an integer offrom about 1 to about 9. Commercially available examples of thesesurfactants include decyl polyglucoside (available as APG® 325 CS) andlauryl polyglucoside (available as APG® 600CS and 625 CS), all theabove-identified polyglucosides are available from Cognis, Ambler, Pa.Also useful herein are sucrose ester surfactants such as sucrose cocoateand sucrose laurate.

Other nonionic surfactants suitable for use in the present invention areglyceryl esters and polyglyceryl esters, including but not limited to,glyceryl monoesters, preferably glyceryl monoesters of C₁₆-C₂₂saturated, unsaturated and branched chain fatty acids such as glyceryloleate, glyceryl monostearate, glyceryl monoisostearate, glycerylmonopalmitate, glyceryl monobehenate, and mixtures thereof, andpolyglyceryl esters of C₁₆-C₂₂ saturated, unsaturated and branched chainfatty acids, such as polyglyceryl-4 isostearate, polyglyceryl-3 oleate,polyglyceryl-2 sesquioleate, triglyceryl diisostearate, diglycerylmonooleate, tetraglyceryl monooleate, and mixtures thereof.

Also useful herein as nonionic surfactants are sorbitan esters.Preferable are sorbitan esters of C₁₆-C₂₂ saturated, unsaturated andbranched chain fatty acids. Because of the manner in which they aretypically manufactured, these sorbitan esters usually comprise mixturesof mono-, di-, tri-, etc. esters. Representative examples of suitablesorbitan esters include sorbitan monooleate (e.g., SPAN® 80), sorbitansesquioleate (e.g., Arlacel® 83, Uniqema, Wilmington, Del.), sorbitanmonoisostearate (e.g., CRILL® 6 from Croda, Inc., Edison, N.J.),sorbitan stearates (e.g., SPAN® 60), sorbitan trioleate (e.g., SPAN®85), sorbitan tristearate (e.g., SPAN® 65), sorbitan dipalmitates (e.g.,SPAN® 40), and sorbitan isostearate. Sorbitan monoisostearate andsorbitan sesquioleate are particularly preferred emulsifiers for use inthe present invention.

Also suitable for use herein are alkoxylated derivatives of glycerylesters, sorbitan esters, and alkyl polyglycosides, wherein the alkoxygroups is selected from the group consisting of C₂-C₆ oxides and theirmixtures, with ethoxylated or propoxylated derivatives of thesematerials being the preferred. Nonlimiting examples of commerciallyavailable ethoxylated materials include TWEEN® (ethoxylated sorbitanmono-, di- and/or tri-esters of C₁₂ to C₁₈ fatty acids with an averagedegree of ethoxylation of from about 2 to about 20).

Preferred nonionic surfactants are those formed from a fatty alcohol, afatty acid, or a glyceride with a C₄ to C₃₆ carbon chain, preferably aC₁₂ to C₁₈ carbon chain, more preferably a C₁₆ to C₁₈ carbon chain,derivatized to yield an HLB of at least 8. HLB is understood to mean thebalance between the size and strength of the hydrophilic group and thesize and strength of the lipophilic group of the surfactant. Suchderivatives can be polymers such as ethoxylates, propoxylates,polyglucosides, polyglycerins, polylactates, polyglycolates,polysorbates, and others that would be apparent to one of ordinary skillin the art. Such derivatives may also be mixed polymers of the above,such as ethoxylate/propoxylate species, where the total HLB ispreferably at least 8. Preferably the nonionic surfactants containethoxylate in a molar content of from about 10-25, more preferably fromabout 10-20 moles.

The nonionic surfactant will typically be present in the composition inan amount of from greater than 0% to about 70% by weight, preferablyfrom about 0.1% to about 50% by weight, and more preferably from about1% to about 30% by weight or from about 5% to about 20% by weight, basedon the total weight of the composition.

In general, non-limiting examples of anionic silicones which may be usedin the present invention include silicone carboxylates, siliconephosphates, silicone sulfates, silicone sulfosuccinates, and siliconesulfonates.

Suitable silicone carboxylates may be chosen from water soluble siliconecompounds comprising at least one carboxylic acid group, oil solublesilicone compounds comprising at least one carboxylic acid group,water-dispersible silicone compounds comprising at least one carboxylicacid group, and silicone compounds comprising at least one carboxylicacid group which are soluble in organic solvents. In one embodiment, theat least one silicone compound comprising at least one carboxylic acidgroup further comprises at least one alkoxylated chain, wherein the atleast one alkoxy group may be chosen from terminal alkoxy groups,pendant alkoxy groups, and alkoxy groups which are intercalated in theskeleton of the at least one silicone compound. Non-limiting examples ofat least one alkoxy group include ethylene oxide groups and propyleneoxide groups.

The at least one carboxylic acid group may be chosen from terminalcarboxylic acid groups and pendant carboxylic acid groups. Further, theat least one carboxylic acid may be chosen from carboxylic acid groupsin free acid form, i.e., —COOH, and carboxylic acid groups in salt form,i.e., —COOM, wherein M may be chosen from inorganic cations, such as,for example, potassium cations and sodium cations, and organic cations.

In one embodiment, the at least one silicone compound comprising atleast one carboxylic acid group is chosen from silicone compounds offormula (I) and salts thereof:

wherein: a is an integer ranging from 1 to 100; b is an integer rangingfrom 0 to 500; R, which may be identical or different, are each chosenfrom optionally substituted hydrocarbon groups comprising from 1 to 9carbon atoms, optionally substituted phenyl groups, and groups offormula (II):

wherein: c, d, and e, which may be identical or different, are eachintegers ranging from 0 to 20; EO is an ethylene oxide group; PO is apropylene oxide group; and R″ is chosen from optionally substituteddivalent hydrocarbons, such as alkylene groups and alkenylene groupscomprising from 2 to 22 carbon atoms, and optionally substituteddivalent aromatic groups, such as groups of formula (III):

and groups of formula (IV):

with the proviso that at least one of the R groups is chosen from groupsof formula (II) and with the further proviso that when only one of the Rgroups is chosen from groups of formula (II), the other R groups are notall methyl groups.

Non-limiting examples of the at least one silicone compound includethose commercially available from Noveon under the name Ultrasil® CA-1Silicone and Ultrasil® CA-2 Silicone, both of which correspond toformula (V) below. This silicone carboxylate is sold in the free acidform as an emulsifier and dispersing aid for complexing fatty cationicamines and quaternary amines. Thus, in one embodiment, the at least onesilicone compound is chosen from silicone compounds of formula (V) andsalts thereof:

wherein: a is an integer ranging from 1 to 100; b is an integer rangingfrom 0 to 500; AO is chosen from groups of formula (VI):-(EO)_(c)—(PO)_(d)-(EO)_(e)—  (VI)

wherein: c, d, and e, which may be identical or different, are eachintegers ranging from 0 to 20; EO is an ethylene oxide group; and PO isa propylene oxide group; x is an integer ranging from 0 to 60; R″ ischosen from optionally substituted divalent hydrocarbons, such asalkylene groups and alkenylene groups comprising from 2 to 22 carbonatoms, and optionally substituted divalent aromatic groups, such asgroups of formula (III):

and groups of formula (IV):

Non-limiting examples of the at least one silicone compound includethose described in U.S. Pat. Nos. 5,248,783 and 5,739,371, thedisclosures of which are incorporated herein by reference, and which aresilicone compounds of formula (I).

Suitable silicone phosphates may be chosen from water-soluble siliconecompounds comprising at least one phosphate group, oil soluble siliconecompounds comprising at least one phosphate group, water-dispersiblesilicone compounds comprising at least one phosphate group, and siliconecompounds comprising at least one phosphate group which are soluble inorganic solvents.

In one embodiment, the at least one silicone compound comprising atleast one phosphate group further comprises at least one alkoxylatedchain, wherein the at least one alkoxy group may be chosen from terminalalkoxy groups, pendant alkoxy groups, and alkoxy groups which areintercalated in the skeleton of the at least one silicone compound.Non-limiting examples of at least one alkoxy group include ethyleneoxide groups (“EO”=—CH₂—CH₂—O) and propylene oxide groups (“PO”=C₃H₆O).

The at least one phosphate group may be chosen from terminal phosphategroups and pendant phosphate groups. Further, the at least one phosphategroup may be chosen from groups of formula —O—P(O)(OH)₂, groups offormula —O—P(O)(OH)(OR), and groups of formula —O—P(O)(OR)₂, wherein Rmay be chosen from H, inorganic cations, and organic cations.Non-limiting examples of inorganic cations include alkali metals, suchas, for example, potassium lithium, and sodium. A non-limiting exampleof organic cations is at least one additional silicone compound whichmay be identical to or different from the at least one silicone compoundbonded to the other oxygen of the phosphate group.

In one embodiment, the at least one silicone compound comprising atleast one phosphate group is chosen from silicone compounds of formula(VII):

wherein R¹, which may be identical or different, are each chosen from H,organic cations, inorganic cations, optionally substituted hydrocarbons(such as alkyl groups and alkenyl groups comprising from 1 to 22 carbonatoms), optionally substituted aromatic groups; groups of formula (VIII)and salts thereof:CH₃(CH₂)_(x)—O-(EO)_(c)—(PO)_(d)-(EO)_(e)—CH₂CH₂—  (VIII)

wherein: c, and d, which may be identical or different, are eachintegers ranging from 0 to 20; e is an integer ranging from 0 to 19; andx is an integer ranging from 0 to 21; groups of formula (IX) and saltsthereof:HO-(EO)_(c)—(PO)_(d)-(EO)_(e)—(CH₂)_(x)—  (IX)

wherein: c, d, and e, which may be identical or different, are eachintegers ranging from 0 to 20; and x is an integer ranging from 0 to 21;and groups of formula (X) and salts thereof:

wherein: a is an integer ranging from 0 to 200; b is an integer rangingfrom 0 to 200; R′, which may be identical or different, are each chosenfrom optionally substituted hydrocarbons, such as alkyl groups andalkenyl groups comprising from 1 to 22 carbon atoms, optionallysubstituted aromatic groups, groups of formula (IX) as defined above andsalts thereof; and R, which may be identical or different, are eachchosen from optionally substituted hydrocarbons, such as alkyl groupsand alkenyl groups comprising from 1 to 22 carbon atoms, optionallysubstituted aromatic groups, optionally substituted divalenthydrocarbons, such as alkylene groups and alkenylene groups comprisingfrom 1 to 22 carbon atoms, optionally substituted divalent aromaticgroups, groups of formula (IX) as defined above and salts thereof, andgroups of formula (XI):-(EO)_(c)—(PO)_(d)-(EO)_(e)—(CH₂)₃—  (XI)wherein:

the (CH₂)₃ end is bonded to the silicon of the compound of formula (X)and the (EO) or (PO) end, if present, is bonded to the oxygen of thecompound of formula (VII); c, d, and e, which may be identical ordifferent, are each integers ranging from 0 to 20; EO is an ethyleneoxide group; and PO is a propylene oxide group; and with the provisothat at least one R is chosen from groups of formula (XI) and saltsthereof; and with the further proviso that at least one R¹ is chosenfrom groups of formula (X) and salts thereof and at least one other R¹is chosen from H, organic cations, and inorganic cations.

Non-limiting examples of the inorganic cations include alkali metals,such as potassium, lithium, and sodium. Non-limiting examples of the atleast one silicone compound include those commercially available fromPhoenix Chemical, Inc. of New Jersey under the name of Pecosil®, such asPecosil® PS-100, Pecosil® PS-112, Pecosil® PS-150, Pecosil® PS-200,Pecosil® WDS-100, Pecosil® WDS-200, Pecosil® PS-100 B, and Pecosil®PS-100 K and those commercially available from Siltech under the nameSilphos A-100 and Silphos A-150. Other non-limiting examples of the atleast one silicone compound include those described in U.S. Pat. Nos.5,070,171, 5,093,452, and 5,149,765 the disclosures of which areincorporated herein by reference.

Suitable silicone sulfates for use in the present invention includethose represented by formula XII:

wherein R¹¹ is selected from lower alkyl having one to eight carbonatoms or phenyl, R¹² is —(CH₂)₃—O-(EO)_(x)—(PO)_(y)-(EO)_(z)—SO₃ ³¹-M⁺wherein M is a cation and is selected from Na, K, Li, or NH₄; x, y and zare integers independently ranging from 0 to 100; R¹³ is—(CH₂)₃—O-(EO)_(x)—(PO)_(y)-(EO)—H; R¹⁴ is methyl or hydroxyl; a¹ and c¹are independently integers ranging from 0 to 50; b¹ is an integerranging from 1 to 50. An example thereof is Ultrasil SA-1 siliconecommercially available from Noveon.

Suitable silicone sulfosuccinates which may be employed include, but arenot limited to, those corresponding to formula XIII:

wherein R represents a divalent radical selected from

wherein a′ and b′ range from 0 to 30; x and y are such that themolecular weight ranges from 700 to 1600, and M is an alkali metal suchas sodium or potassium, or an ammonium group.

A particularly preferred anionic silicone is Dimethicone PEG-7phosphate, commercially available from Phoenix Chemical under thetradenames Pecosil® PS-100 and Pecosil® PS-112, and from LubrizolAdvanced Materials, Inc. under the tradename Silsense® PE-100L Silicone.Another particularly preferred anionic silicone is Dimethicone PEG-8phosphate, commercially available from Lubrizol Advanced Materials, Inc.under the tradename Silsense® PE-100 Silicone.

The anionic silicone is present in the composition in an amount rangingfrom greater than 0% to about 50% by weight, preferably about 0.1% toabout 30% by weight, and more preferably from about 0.5% to about 15% byweight, based on the weight of the composition as a whole.

Dye Compounds

The dye compounds of the present disclosure may be chosen from oxidationbases, couplers, and direct dyes.

Oxidation Bases

Examples of oxidation bases include ortho or para aminophenols, ortho orpara phenylenediamines, double bases, heterocyclic bases, and the acidaddition salts thereof.

The para-phenylenediamines which can be used include compounds of thefollowing formula (A) and their addition salts with an acid:

in which:

R₈ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical, a C₁-C₄ alkyl radical substituted bya nitrogenous group, a phenyl radical or a 4′-aminophenyl radical;

R₉ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ radical substituted by anitrogenous group;

R₈ and R₉ can also form, with the nitrogen atom which carries them, a 5-or 6-membered nitrogenous heterocycle optionally substituted by one ormore alkyl, hydroxyl or ureido groups;

R₁₀ represents a hydrogen atom, a halogen atom, such as a chlorine atom,a C₁-C₄ alkyl radical, a sulpho radical, a carboxyl radical, a C₁-C₄monohydroxyalkyl radical, a C₁-C₄ hydroxyalkoxy radical, a C₁-C₄acetylaminoalkoxy radical, a C₁-C₄ mesylaminoalkoxy radical or C₁-C₄carbamoylaminoalkoxy radicals;

R₁₁ represents a hydrogen atom, a halogen atom or a C₁-C₄ alkyl radical.

The nitrogenous groups in the above formula (A) include amino,mono(C₁-C₄)alkylamino, di(C₁-C₄)alkylamino, tri(C₁-C₄)alkylamino,monohydroxy(C₁-C₄)alkylamino, imidazolinium and ammonium radicals.

The para-phenylenediamines of above formula (A) includepara-phenylenediamine, para-toluoylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline,2-(β-hydroxyethyl)-para-phenylenediamine,2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-(β-hydroxyethyloxy)-para-phenylenediamine,2-(β-acetylaminoethyloxy)-para-phenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine,2-methyl-1-N-(β-hydroxyethyl)-para-phenylenediamine and their additionsalts with an acid.

In one embodiment, the para-phenylenediamines of above formula (A)include para-phenylenediamine, para-toluoylenediamine,2-isopropyl-para-phenylenediamine,2-(β-hydroxyethyl)-para-phenylenediamine,2-(β-hydroxyethyloxy)-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine and their addition salts with an acid.

The ortho-phenylenediamines includeN1-(2-hydroxyethyl)-4-nitro-o-phenylenediamine,4-methyl-o-phenylenediamine, and 4-nitro-o-phenylenediamine and acidaddition salts thereof.

As used herein, the term “double bases” means compounds comprising atleast two aromatic nuclei having at least one of amino and hydroxylgroups.

Examples include compounds corresponding to the following formula (B)and their addition salts with an acid:

in which:

Z₁ and Z₂, which are identical or different, represent a hydroxyl or—NH₂ radical which can be substituted by a C₁-C₄ alkyl radical or by aconnecting arm Y;

the connecting arm Y represents a linear or branched alkylene chaincomprising from 1 to 14 carbon atoms which can be interrupted orterminated by one or more nitrogenous groups and/or by one or moreheteroatoms, such as oxygen, sulphur or nitrogen atoms, and which isoptionally substituted by one or more hydroxyl or C₁-C₆ alkoxy radicals;

R₁₂ and R₁₃ represent a hydrogen or halogen atom, a C₁-C₄ alkyl radical,a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, aC₁-C₄ aminoalkyl radical or a connecting arm Y;

R₁₄, R₁₅, R₁₆, R₁₇, R₁₈ and R₁₉, which are identical or different,represent a hydrogen atom, a connecting arm Y or a C₁-C₄ alkyl radical;

it is being understood that the compounds of formula (B) only comprise asingle connecting arm Y per molecule.

Nitrogenous groups of the above formula (B) include amino,mono(C₁-C₄)alkylamino, di(C₁-C₄)alkylamino, tri(C₁-C₄)alkylamino,monohydroxy(C₁-C₄)alkylamino, imidazolinium and ammonium radicals.

Additional examples of double bases of above formula (B) include ofN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino-propanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)-tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-diethyl-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane and their addition saltswith an acid.

In one embodiment the double base isN,N′-Bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane or one of their additionsalts with an acid.

The para-aminophenols which can be used include compounds of thefollowing formula (C) and their addition salts with an acid:

in which:

R₂₀ represents a hydrogen atom, a halogen atom, such as fluorine, aC₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical, a C₁-C₄ aminoalkyl radical or ahydroxy(C₁-C₄)alkylamino-(C₁-C₄)alkyl radical,

R₂₁ represents a hydrogen atom, a halogen atom, such as fluorine, aC₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄polyhydroxyalkyl radical, a C₁-C₄ aminoalkyl radical, a C₁-C₄ cyanoalkylradical or a (C₁-C₄)alkoxy(C₁-C₄)alkyl radical.

Among the para-aminophenols, mention may be made of para-aminophenol,4-amino-3-methylphenol, 4-amino-3-fluorophenol,4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,4-amino-2-hydroxymethyl phenol, 4-amino-2-methoxymethylphenol,4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol, N-methyl-para-aminophenol,and the acid addition salts thereof.

The ortho-aminophenols that may be used as oxidation bases in thecontext of certain embodiments may be chosen from 2-aminophenol,2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6-methylbenzene,5-acetamido-2-aminophenol, and the acid addition salts thereof.

Heterocyclic bases that can be used as oxidation bases in the methods ofcoloring keratinous substrates include pyridine derivatives, pyrimidinederivatives, pyrazole derivatives, pyrazolinone derivatives, and theacid addition salts thereof.

Pyridine derivatives include the compounds described, for example, inpatents GB 1,026,978 and GB 1,153,196, as well as the compounds2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine,2,3-diamino-6-methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6methoxypyridine, 3,4-diaminopyridine, and the acid addition saltsthereof.

Pyrimidine derivatives include the compounds disclosed, for example, inGerman Patent DE 2 359 399 or Japanese Patents JP 88-169 571 and JP91-10659 or Patent Application WO 96/15765, such as2,4,5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triamino-pyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and thepyrazolopyrimidine derivatives, such as those mentioned in FrenchApplication FR-A-2 750 048 and among which may be mentionedpyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;pyrazolo[1,5-a]pyrimidine-3,5-diamine;2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;3-aminopyrazolo[1,5-a]pyrimidin-7-ol;3-aminopyrazolo[1,5-a]pyrimidin-5-ol;2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol;2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol;5,6-dimethyl-pyrazolo[1,5-a]pyrimidine-3,7-diamine;2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;3-amino-5-methyl-7-(imidazolylpropylamino)pyrazolo[1,5-a]pyrimidine; andtheir addition salts and their tautomeric forms, when there exists atautomeric equilibrium, and their addition salts with an acid.

Pyrazole and pyrazolinone derivatives include the compounds described inpatents DE 3,843,892, DE 4,133,957 and patent applications WO 94/08969,WO 94/08970, FR-A-2,733,749, and DE 195 43 988, such as4,5-diamino-1-methyl-pyrazole, 3,4-diaminopyrazole,4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)pyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(R-hydroxyethyl)amino-1-methylpyrazole,2-(4,5-diamino-1H-pyrazol-1-yl), H₂SO₄,2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-z]pyrazol-1-one,1-methyl-3-phenyl-2-pyrazolinone, and the acid addition salts thereof.

Even further non-limiting mentions can be made of2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/oraddition salts thereof.

As heterocyclic bases, further non-limiting mentions can be made of4,5-diamino-1-(R-hydroxyethyl)pyrazole and/or2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/oraddition salts thereof.

As cationic oxidation bases usable in the ready-to-use compositionsaccording to the disclosure, non-limiting mentions can be made of thefollowing compounds: the para-phenylenediamines for example as describedin French Patent Application Nos. 2 766 177 and 2 766 178, thepara-aminophenols as described for example in French Patent ApplicationNos. 2 766 177 and 2 766 178, the ortho-phenylenediamines as describedfor example in French Patent Application Nos. 2 782 718, 2 782 716 and 2782 719, the ortho-aminophenols or cationic double bases such asderivatives of the bis(aminophenyl)alkylenediamine type described inFrench Patent Application No. 2 766 179, as well as the cationicheterocyclic bases, the compounds bearing at least one quaternarynitrogen atom.

For example, the cationic oxidation bases usable in the compositionsaccording to the disclosure are cationic para-phenylenediamines. Forexample, in some embodiments cationic oxidation bases ofpara-phenylenediamine structure can be used, wherein at least one of theamine functions is a tertiary amine bearing a pyrrolidine nucleus, themolecule possessing at least one quaternized nitrogen atom. Such basesare described, for example, in European Patent Application PublicationNo. 1 348 695.

The oxidation bases may be employed in amounts ranging from about0.0001% to about 12% by weight, or from about 0.1% to about 8.0% byweight, or from about 1% to about 5% by weight, based on the totalweight of the composition.

Coupler Compounds

The compositions of the present disclosure may also contain couplercompounds. The couplers that may be used in the dyeing method disclosedherein include those conventionally used in oxidative methods ofcoloring keratinous fibers, for example, meta-aminophenols,meta-phenylenediamines and meta-diphenols, naphthols, mono- orpolyhydroxylated naphthalene derivatives, and heterocyclic couplers suchas, for example, indole derivatives, indoline derivatives, sesamol andits derivatives, pyridine derivatives, pyrazolotriazole derivatives,pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles,1,3-benzodioxoles, quinolines, benzomorpholine derivatives,pyrazoloazole derivatives, pyrroloazole derivatives, imidazoloazolederivatives, pyrazolopyrimidine derivatives, pyrazoline-3,5-dionederivatives, pyrrolo[3,2-d]oxazole derivatives, pyrazolo[3,4-d]thiazolederivatives, thiazoloazole S-oxide derivatives, thiazoloazoleS,S-dioxide derivatives, and the acid addition salts thereof.

Suitable color couplers include, for example, those having the generalformula (D):

wherein R₁ is unsubstituted hydroxy or amino, or hydroxy or aminosubstituted with one or more C₁₋₆ hydroxyalkyl groups, R₃ and R₅ areeach independently hydrogen, hydroxy, amino, or amino substituted withC₁₋₆ alkyl, C₁₋₆ alkoxy, or C₁₋₆ hydroxyalkyl group; and R₂, R₄, and R₆are each independently hydrogen, C₁₋₆ alkoxy, C₁₋₆ hydroxyalkyl, or C₁₋₆alkyl, or R₃ and R₄ together may form a methylenedioxy or ethylenedioxygroup. Examples of such compounds include meta-derivatives such asphenols, meta-aminophenols, meta-phenylenediamines, and the like, whichmay be unsubstituted, or substituted on the amino group or benzene ringwith alkyl, hydroxyalkyl, alkylamino groups, and the like. Suitablecouplers include m-aminophenol, 2,4-diaminotoluene, 4-amino,2-hydroxytoluene, phenyl methyl pyrazolone, 3,4-methylenedioxyphenol,3,4-methylenedioxy-1-[(β-hydroxyethyl)amino]benzene,1-methoxy-2-amino-4-[(β-hydroxyethyl)amino]benzene,1-hydroxy-3-(dimethylamino)benzene,6-methyl-1-hydroxy-3[(β-hydroxyethyl)amino]benzene,2,4-dichloro-1-hydroxy-3-aminobenzene,1-hydroxy-3-(diethylamino)benzene, 1-hydroxy-2-methyl-3-aminobenzene,2-chloro-6-methyl-1-hydroxy-3-aminobenzene, 1,3-diaminobenzene,6-methoxy-1,3-diaminobenzene, 6-hydroxyethoxy-1,3-diaminobenzene,6-methoxy-5-ethyl-1,3-diaminobenzene, 6-ethoxy-1,3-diaminobenzene,1-bis(R-hydroxyethyl)amino-3-aminobenzene, 2-methyl-1,3-diaminobenzene,6-methoxy-1-amino-3-[(β-hydroxyethyl)amino]-benzene,6-(β-aminoethoxy)-1,3-diaminobenzene,6-(β-hydroxyethoxy)-1-amino-3-(methylamino)benzene,6-carboxymethoxy-1,3-diaminobenzene,6-ethoxy-1-bis(3-hydroxyethyl)amino-3-aminobenzene,6-hydroxyethyl-1,3-diaminobenzene,1-hydroxy-2-isopropyl-5-methylbenzene, 1,3-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene, 2-methyl-1,3-dihydroxybenzene,4-chloro-1,3-dihydroxybenzene,5,6-dichloro-2-methyl-1,3-dihydroxybenzene, 1-hydroxy-3-amino-benzene,1-hydroxy-3-(carbamoylmethylamino)benzene, 6-hydroxybenzomorpholine,4-methyl-2,6-dihydroxypyridine, 2,6-dihydroxypyridine,2,6-diaminopyridine, 6-aminobenzomorpholine,1-phenyl-3-methyl-5-pyrazolone, 1-hydroxynaphthalene,1,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 5-amino-2-methylphenol, 4-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindole,6-hydroxyindoline, 2,4-diamionphenoxyethanol, and mixtures thereof.

Other couplers may be chosen, for example, from2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol,5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxybenzene, 2,4-diamino 1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol,1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole,6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine,1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,6-methylpyrazolo[1,5-a]-benzimidazole, and the acid addition saltsthereof.

In one embodiment, the couplers include resorcinol, 1-naphthol,2-methylresorcinol, 4-amino-2-hydroxy toluene, m-aminophenol,2,4-diaminophenoxyethanol, phenyl methyl pyrazolone,hydroxybenzomorpholine, 2-methyl-5-hydroxyethylaminophenol,6-hydroxyindole, 2-amino-3-hydroxypyridine, 5-amino-6-chloro-o-cresol,4-chlororesorcinol, their salts, and mixtures thereof.

When they are present, couplers may be present in amounts ranging fromabout 0.0001% to about 12% by weight; or from about 0.1% to about 8% byweight; or from about 1% to about 5% based on the total weight of thecomposition.

In general, the acid addition salts of the oxidation bases and couplersmay be chosen from hydrochlorides, hydrobromides, sulphates, tartrates,lactates, and acetates.

Direct Dyes

A direct dye is a colored substance that does not require the use of anoxidizing agent in order to reveal its color. Suitable direct dyes whichmay be used according to the present invention may be chosen from acidic(anionic), basic (cationic), and neutral dyes.

“Acidic dye” is generally intended to mean a dye containing at least oneCOOH, SO₃H, PO₃H, or PO₄H₂ group, it being possible for said groups toexist in the form of salts. “Salts” is generally intended to mean saltsof metals (for example, alkali metals or alkaline earth metals), saltsof an organic amine that is optionally hydroxylated. Such dyes are alsoreferred to as anionic dyes.

The acidic dyes that can be used in the context of this invention can bechosen from acidic nitro dyes, acidic azo dyes, acidic azine dyes,acidic triarylmethane dyes, acidic quinone dyes, acidic indo-amine dyesand acidic natural dyes, and mixtures thereof.

“Basic dyes” is generally intended to mean a dye that has at least onegroup bearing a positive charge, such as an ammonium group or aquaternized nitrogen atom in a ring. Such dyes are also referred to ascationic dyes.

The basic dyes that can be used in the context of this invention can bechosen from nitrobenzene dyes, azo dyes, azomethine dyes, methine dyes,tetraazapentamethine dyes, anthraquinone dyes, naphthoquinone dyes,benzoquinone dyes, phenothiazine dyes, indigoid dyes, xanthene dyes,phenanthridine dyes, phthalocyanin dyes, triarylamethane-derived dyesand basic natural dyes, and mixtures thereof.

Preferably, the direct dyes may be present in amounts ranging from about0.001% to about 30% by weight, preferably from about 0.01% to about 20%by weight, more preferably from about 0.1% to about 10% by weight, andeven more preferably from about 1% to about 5% by weight, based on thetotal weight of the composition.

Thickening Agent

Thickening agents of the present invention may be chosen from polymericthickeners and non-polymeric thickeners as described in US2010154140A,herein incorporated by reference in its entirety.

Thickening agents of the present invention may be chosen from polymericthickeners and non-polymeric thickeners. The at least one polymericthickener can be ionic or non-ionic, associative or non-associativepolymer. Exemplary polymeric thickeners include various native gums.Representative non-polymeric thickening agents include mineral saltssuch as sodium chloride; oxyethylenated molecules and especiallyethoxylated alkyl or acyl derivatives of polyols. These polymers can bemodified physically or chemically.

In the present invention, the thickening agent is preferably used in anamount of from greater than 0% to about 15% by weight, preferably fromabout 0.1% to about 10% by weight, and more preferably from about 0.5%to about 5% by weight, and even more preferably from about 1% to about4% by weight, based on the total weight of the composition.

Alkaline Agents

The at least one alkaline agent of the present invention may be chosenfrom organic amines, organic amine salts, ammonium salts, and inorganicbases.

The organic amines may be chosen from the ones having a pKb at 25° C. ofless than 12, such as less than 10 or such as less than 6. It should benoted that this is the pKb corresponding to the function of highestbasicity.

Organic amines may be chosen from organic amines comprising one or twoprimary, secondary, or tertiary amine functions, and at least one linearor branched C₁-C₈ alkyl groups bearing at least one hydroxyl radical.

Organic amines may also be chosen from alkanolamines such as mono-, di-or trialkanolamines, comprising one to three identical or differentC₁-C₄ hydroxyalkyl radicals, ethylamines, ethyleneamines, quinoline,aniline and cyclic amines, such as pyrroline, pyrrole, pyrrolidine,imidazole, imidazolidine, imidazolidinine, morpholine, pyridine,piperidine, pyrimidine, piperazine, triazine and derivatives thereof.

Among the compounds of the alkanolamine type that may be mentionedinclude but not limited to: monoethanolamine, diethanolamine,triethanolamine, monoisopropanolamine, diisopropanolamine,N-dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol,triisopropanolamine, 2-amino-2-methyl-1,3-propanediol,3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, andtris(hydroxymethylamino)methane.

The organic amines correspond to formula XIV:

wherein W is chosen from C₁-C₆ alkylene residues optionally substitutedwith a hydroxyl group or a C₁-C₆ alkyl radical; Rx, Ry, Rz and Rt, whichmay be identical or different, are chosen from a hydrogen atom, C₁-C₆alkyl radicals, C₁-C₆ hydroxyalkyl radicals, and C₁-C₆ aminoalkylradicals.

Examples of such amines that may be mentioned include but not limitedto: 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine, andspermidine.

In some embodiments, the organic amines are chosen from amino acids.

As non-limiting examples, the amino acids that may be used may be ofnatural or synthetic origin, in L, D, or racemic form, and comprise atleast one acid function chosen from, for instance, carboxylic acid,sulfonic acid, phosphonic acid, and phosphoric acid functions. The aminoacids may be in their neutral or ionic form.

Further as non-limiting examples, the amino acids may be chosen frombasic amino acids comprising an additional amine function optionallyincluded in a ring or in a ureido function.

Such basic amino acids may be chosen from those corresponding to formula(E) below:

wherein R is a group chosen from:

The compounds corresponding to formula (E) may be chosen from histidine,lysine, arginine, ornithine, and citrulline.

Amino acids that may be used in the present disclosure include but notlimited to: aspartic acid, glutamic acid, alanine, arginine, ornithine,citrulline, asparagine, carnitine, cysteine, glutamine, glycine,histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine,proline, serine, taurine, threonine, tryptophan, tyrosine, and valine.

In some embodiments, the organic amines are chosen from basic aminoacids. The amino acids may be chosen from, for instance, arginine,lysine and histidine, or mixtures thereof.

In some embodiments, the organic amines are chosen from organic aminesof heterocyclic type. Besides histidine that has already been mentionedin the amino acids, non-limiting mention may also be made of pyridine,piperidine, imidazole, 1,2,4-triazole, tetrazole, and benzimidazole.

In some embodiments, the organic amines are chosen from amino aciddipeptides. Amino acid dipeptides that may be used in the presentdisclosure include but not limited to: carnosine, anserine, and baleine.

In some embodiments, the organic amines are chosen from compoundscomprising a guanidine function. Organic amines of this type that may beused in the present disclosure include, besides arginine that hasalready been mentioned as an amino acid, creatine, creatinine,1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin,agmatine, N-amidinoalanine, 3-guanidinopropionic acid,4-guanidinobutyric acid, and2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

As a non-limiting example, the organic amines are chosen fromalkanolamines. For example, the organic amines are chosen from2-amino-2-methyl-1-propanol and monoethanolamine, or mixtures thereof.Further as an example, the organic amine is monoethanolamine.

The alkaline agent may be an organic amine in salt form. The term“organic amine salt,” as used herein, means organic or mineral salts ofan organic amine as described above.

As a non-limiting example, the organic salts may be chosen from thesalts of organic acids, such as citrates, lactates, glycolates,gluconates, acetates, propionates, fumarates, oxalates and tartrates.

Further as a non-limiting example, the mineral salts may be chosen fromhydrohalides (for example hydrochlorides), carbonates, hydrogencarbonates, sulfates, hydrogen phosphates, and phosphates.

The ammonium salts that may be used in the composition according to thepresent disclosure may be chosen from the following acid salts:carbonate, bicarbonate. For instance, the salt is the carbonate, such asammonium carbonate.

The inorganic bases that may be used in the composition according to thepresent disclosure may be chosen from alkali metal phosphates andcarbonates such as, for example, sodium phosphate, potassium phosphate,sodium carbonate, sodium bicarbonate, potassium carbonate, potassiumbicarbonate, and their derivatives.

The inorganic bases may also include alkali metals of carboxylates suchas, for example, sodium acetate, potassium acetate, sodium citrate, andpotassium citrate, and their derivatives.

According to one embodiment, the ready-to-use composition of the presentinvention comprises an alkaline agent chosen from at least one organicamine such as at least one alkanolamine. When the composition comprisesmore than one alkaline agents including an alkanolamine andammoniumhydroxides or salts thereof, the amount of organic amine(s) arefor example higher than the amount of ammonia.

According to another embodiment, the ready-to-use composition of thepresent invention is substantially free of ammonia. The term“substantially free of ammonia” means that the composition of thepresent invention is either completely free of ammonia (includingammonium ions) or contains no appreciable amount of ammonia (includingammonium ions), for example, no more than 1% by weight, or no more than0.5% by weight, or no more than 0.3% by weight, or no more than 0.1% byweight, based on the weight of the composition. According to thisembodiment, the ready-to-use composition, for example, contains at leastone alkanolamine such as monoethanolamine.

The at least one alkaline agent may be employed in the composition ofthe present invention in an amount ranging from about 0.001% to about30% by weight, such as from about 0.01% to about 20% by weight or fromabout 0.1% to about 15% by weight, or from about 1% to about 10% byweight, based on the total weight of the composition.

Fatty Substance

The composition of the present invention may further comprise at leastone fatty substance other than a fatty acid.

“Fatty substance” means an organic compound insoluble in water at normaltemperature (25° C.) and at atmospheric pressure (760 mmHg) (solubilitybelow 5% and such as below 1% and further such as below 0.1%). Fattysubstances have in their structure a chain of at least two siloxanegroups or at least one hydrocarbon chain having at least 6 carbon atoms.Moreover, fatty substances are generally soluble in organic solvents inthe same conditions of temperature and pressure, for example inchloroform, ethanol, benzene or decamethylcyclopentasiloxane.

The composition of the present invention comprises at least 10% of fattysubstances by weight relative to the total weight of the composition,these substances being other than fatty acid.

Fatty substances are, for example, chosen from lower alkanes, fattyalcohols, esters of fatty acid, esters of fatty alcohol, oils such asmineral, vegetable, animal and synthetic non-silicone oils, non-siliconewaxes and silicones.

In some embodiments, the alcohols and esters have at least one linear orbranched, saturated or unsaturated hydrocarbon group, comprising 6 to 30carbon atoms, optionally substituted, for example, with at least onehydroxyl group (for example 1 to 4). If they are unsaturated, thesecompounds can have one to three, conjugated or unconjugated,carbon-carbon double bonds.

With regard to the lower alkanes, in some embodiments, these have from 6to 16 carbon atoms and are linear or branched, optionally cyclic. Asexamples, alkanes can be chosen from hexane and dodecane, isoparaffinssuch as isohexadecane and isodecane.

Non-limiting examples of non-silicone oils usable in the composition ofthe disclosure, include: hydrocarbon oils of animal origin, such asperhydrosqualene; hydrocarbon oils of vegetable origin, such as liquidtriglycerides of fatty acids having from 6 to 30 carbon atoms such astriglycerides of heptanoic or octanoic acids, or for example sunfloweroil, maize oil, soya oil, cucurbit oil, grapeseed oil, sesame oil,hazelnut oil, apricot oil, macadamia oil, arara oil, sunflower oil,castor oil, avocado oil, triglycerides of caprylic/capric acids such asthose sold by the company Stearineries Dubois or those sold under thenames MIGLYOL® 810, 812 and 818 by the company Dynamit Nobel, jojobaoil, shea butter oil; hydrocarbons with more than 16 carbon atoms,linear or branched, of mineral or synthetic origin, such as paraffinoils, petroleum jelly, liquid paraffin, polydecenes, hydrogenatedpolyisobutene such as Parleam®. fluorinated, partially hydrocarbon oils;as fluorinated oils, non-limiting examples includeperfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, soldunder the names “FLUTEC® PC1” and “FLUTEC® PC3” by the company BNFLFluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanessuch as dodecafluoropentane and tetradecafluorohexane, sold under thenames “PF 5050®” and “PF 5060®” by the 3M Company, orbromoperfluorooctyl sold under the name “FORALKYL®” by the companyAtochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane;derivatives of perfluoromorpholine, such as 4-trifluoromethylperfluoromorpholine sold under the name “PF 5052®” by the 3M Company.

The fatty alcohols usable as fatty substances in the composition of thedisclosure include, but are not limited to, non-alkoxylated, saturatedor unsaturated, linear or branched, and have from 6 to 30 carbon atomsand more particularly from 8 to 30 carbon atoms; For example, cetylalcohol, stearyl alcohol and their mixture (cetylstearyl alcohol),octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol,oleic alcohol or linoleic alcohol.

The exemplary non-silicone wax or waxes that can be used in thecomposition of the disclosure are chosen from carnauba wax, candelillawax, and Alfa wax, paraffin wax, ozokerite, vegetable waxes such asolive wax, rice wax, hydrogenated jojoba wax or absolute waxes offlowers such as the essential wax of blackcurrant flower sold by thecompany BERTIN (France), animal waxes such as beeswaxes, or modifiedbeeswaxes (cerabellina); other waxes or waxy raw materials usableaccording to the disclosure are, for example, marine waxes such as thatsold by the company SOPHIM under reference M82, waxes of polyethylene orof polyolefins in general.

The exemplary fatty acid esters are the esters of saturated orunsaturated, linear or branched C₁-C₂₆ aliphatic mono- or polyacids andof saturated or unsaturated, linear or branched C₁-C₂₆ aliphatic mono-or polyalcohols, the total number of carbons of the esters being, forexample, greater than or equal to 10.

Among the monoesters, non-limiting mentions can be made ofdihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyllactate; C₁₂-C₁₅ alkyl lactate; isostearyl lactate; lauryl lactate;linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyloctanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetylisostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate;isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexylisononate; octyl palmitate; octyl pelargonate; octyl stearate;octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates,ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates suchas isopropyl, butyl, cetyl, 2-octyldodecyl, mirystyl, stearyl myristate,hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyllaurate, and 2-hexyldecyl laurate.

Further non-limiting mentions of esters can be made of the esters ofC₄-C₂₂ di- or tricarboxylic acids and of C₁-C₂₂ alcohols and the estersof mono-, di- or tricarboxylic acids and of C₂-C₂₆ di-, tri-, tetra- orpentahydroxy alcohols.

Even further non-limiting examples of esters include: diethyl sebacate;diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyladipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate;octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate;pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate;pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate;propylene glycol dicaprylate; propylene glycol dicaprate, tridecylerucate; triisopropyl citrate; triisotearyl citrate; glyceryltrilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleylcitrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate;diethylene glycol diisanonate; and polyethylene glycol distearates.

Among the esters mentioned above, exemplary esters include ethyl,isopropyl, myristyl, cetyl, stearyl palmitates, ethyl-2-hexyl palmitate,2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl,cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate,isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurateand isononyl isononanate, cetyl octanoate.

The composition can also comprise, as fatty ester, esters and di-estersof sugars of C₆-C₃₀, such as C₁₂-C₂₂ fatty acids. “Sugar” as used in thedisclosure means oxygen-containing hydrocarbon compounds that possessseveral alcohol functions, with or without aldehyde or ketone functions,and having at least 4 carbon atoms. These sugars can be monosaccharides,oligosaccharides or polysaccharides.

As suitable sugars, non-limiting examples include sucrose, glucose,galactose, ribose, fucose, maltose, fructose, mannose, arabinose,xylose, lactose, and their derivatives, for example alkylated, such asmethylated derivatives such as methylglucose.

The esters of sugars and of fatty acids can, for example, be chosen fromthe esters or mixtures of esters of sugars described previously and oflinear or branched, saturated or unsaturated C₆-C₃₀, such as C₁₂-C₂₂fatty acids. If they are unsaturated, these compounds can have one tothree, conjugated or unconjugated, carbon-carbon double bonds.

The esters according to at least one embodiment can also be chosen frommono-, di-, tri- and tetra-esters, polyesters and mixtures thereof.

These esters can be for example oleate, laurate, palmitate, myristate,behenate, cocoate, stearate, linoleate, linolenate, caprate,arachidonates, or mixtures thereof such as the oleo-palmitate,oleo-stearate, palmito-stearate mixed esters.

For example, the mono- and di-esters can be used, and such as the mono-or di-oleate, stearate, behenate, oleopalmitate, linoleate, linolenate,oleostearate, of sucrose, of glucose or of methylglucose.

Non-limiting mention can be made of the product sold under the nameGLUCATE® DO by the company Amerchol, which is a dioleate ofmethylglucose.

Exemplary esters or of mixtures of esters of sugar of fatty acidinclude: the products sold under the names F160, F140, F110, F90, F70,SL40 by the company Crodesta, denoting respectively thepalmito-stearates of sucrose formed from 73% of monoester and 27% of di-and tri-ester, from 61% of monoester and 39% of di-, tri-, andtetra-ester, from 52% of monoester and 48% of di-, tri-, andtetra-ester, from 45% of monoester and 55% of di-, tri-, andtetra-ester, from 39% of monoester and 61% of di-, tri-, andtetra-ester, and the mono-laurate of sucrose; the products sold underthe name Ryoto Sugar Esters for example with the reference B370 andcorresponding to the behenate of sucrose formed from 20% of monoesterand 80% of di-triester-polyester; sucrose mono-di-palmito-stearatemarketed by the company Goldschmidt under the name TEGOSOFT® PSE.

The silicones usable in the composition of the present disclosureinclude but are not limited to volatile or non-volatile, cyclic, linearor branched silicones, modified or not with organic groups, having aviscosity from 5×10⁻⁶ to 2.5 m²/s at 25° C., such as from 1×10⁻⁵ to 1m²/s.

The silicones usable according to the disclosure can be in the form ofoils, waxes, resins or gums.

In some embodiments, the silicone is chosen from thepolydialkylsiloxanes, such as the polydimethylsiloxanes (PDMS), and theorgano-modified polysiloxanes having at least one functional groupselected from the poly(alkoxylated) groups, the amine groups and thealkoxy groups.

The organopolysiloxanes are defined in more detail in the work of WalterNOLL “Chemistry and Technology of Silicones” (1968), Academic Press.They can be volatile or non-volatile.

When they are volatile, the silicones are, for example, chosen fromthose with a boiling point between 60° C. and 260° G and for furtherexamples, chosen from:

the cyclic polydialkylsiloxanes having from 3 to 7, such as from 4 to 5silicon atoms. It can be, for example, the octamethylcyclotetrasiloxanemarketed under the name VOLATILE SILICONE® 7207 by UNION CARBIDE orSILBIONE® 70045 V2 by RHODIA, the decamethylcyclopentasiloxane marketedunder the name VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBIONE®70045 V5 by RHODIA, and mixtures thereof.

Non-limiting mentions can also be made of the cyclocopolymers of thedimethylsiloxanes/methylalkylsiloxane type, such as SILICONE VOLATILE®FZ 3109 marketed by the company UNION CARBIDE, of the formula XV:

with D″:

Non-limiting mentions can further be made of the mixtures of cyclicpolydialkylsiloxanes with organic compounds derived from silicon, suchas the mixture of octamethylcyclotetrasiloxane andtetratrimethylsilylpentaerythritol (50/50) and the mixture ofoctamethylcyclotetrasiloxane andoxy-1,1′-(hexa-2,2,2′,2′,3,3′-trimethylsilyloxy)bis-neopentane.

Other suitable volatile silicones include the linear volatilepolydialkylsiloxanes having 2 to 9 silicon atoms and with a viscosityless than or equal to 5×10⁻⁶ m²/s at 25° C. An example isdecamethyltetrasiloxane, marketed under the name “SH 200” by the companyTORAY SILICONE. Silicones included in this class are also described inthe article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, p.27-32—TODD BYERS “Volatile Silicone fluids for cosmetics”.

Even further non-limiting mentions can be made of non-volatilepolydialkylsiloxanes, gums and resins of polydialkylsiloxanes,polyorganosiloxanes modified with the aforementioned organofunctionalgroups, and mixtures thereof.

These silicones are, for example, chosen from the polydialkylsiloxanes,such as the polydimethylsiloxanes with trimethylsilyl end groups. Theviscosity of the silicones is measured at 25° C. according to StandardTest Method for Kinematic Viscosity of Transparent and Opaque Liquids(and Calculation of Dynamic Viscosity)

Among these polydialkylsiloxanes, mention can be made of,non-exhaustively, the following commercial products: the SILBIONE® oilsof series 47 and 70 047 or the MIRASIL® oils marketed by RHODIA, forexample the oil 70 047 V 500 000; the oils of the MIRASIL® seriesmarketed by the company RHODIA; the oils of the 200 series from thecompany DOW CORNING such as DC200, with a viscosity of 60 000 mm²/s; theVISCASIL® oils from GENERAL ELECTRIC and certain oils of the SF series(SF 96, SF 18) from GENERAL ELECTRIC.

Non-limiting mention can also be made of the polydimethylsiloxanes withdimethylsilanol end groups known under the name of dimethiconol (CTFA),such as the oils of the 48 series from the company RHODIA.

In this class of polydialkylsiloxanes, non-limiting mentions can be madeof the products marketed under the names “ABIL WAX® 9800 and 9801” bythe company GOLDSCHMIDT, which are polydialkyl(C₁-C₂₀) siloxanes.

The silicone gums usable according to the disclosure are, for example,polydialkylsiloxanes, such as polydimethylsiloxanes with highnumber-average molecular weights between 200,000 and 1,000,000 usedalone or mixed in a solvent. This solvent can be chosen from thevolatile silicones, the polydimethylsiloxane (PDMS) oils, thepolyphenylmethylsiloxane (PPMS) oils, the isoparaffins, thepolyisobutylenes, methylene chloride, pentane, dodecane, tridecane andmixtures thereof.

Products usable according to the disclosure are, for example, mixturessuch as: mixtures formed from a chain end hydroxylatedpolydimethylsiloxane, or dimethiconol (CTFA) and a cyclicpolydimethylsiloxane also called cyclomethicone (CTFA), such as theproduct Q2 1401 marketed by the company DOW CORNING; mixtures of apolydimethylsiloxane gum and a cyclic silicone such as the product SF1214 Silicone Fluid from the company GENERAL ELECTRIC, said productbeing a gum SF corresponding to a dimethicone, having a number-averagemolecular weight of 500,000, dissolved in the oil SF 1202 Silicone Fluidcorresponding to decamethylcyclopentasiloxane; mixtures of two PDMS ofdifferent viscosities, for example, of a PDMS gum and a PDMS oil, suchas the product SF 1236 from the company GENERAL ELECTRIC. The product SF1236 is a mixture of a gum SE 30 as defined above having a viscosity of20 m²/s and an oil SF 96 with a viscosity of 5×10⁻⁶ m2/s. This product,for example, has 15% of gum SE 30 and 85% of oil SF 96.

The organopolysiloxane resins usable according to the disclosure includebut are not limited to crosslinked siloxane systems containing theunits: R₂SiO_(2/2), R₃SiO_(1/2), RSiO_(3/2) and SiO_(4/2)

in which R represents an alkyl having 1 to 16 carbon atoms. For example,R denotes a C₁-C₄ lower alkyl group such as methyl.

Among these resins, non-limiting mention can be made of the productmarketed under the name “DOW CORNING® 593” or those marketed under thenames “SILICONE FLUID SS 4230 and SS 4267” by the company GENERALELECTRIC, which are silicones of dimethyl/trimethyl siloxane structure.

Non-limiting mention can also be made of the resins of thetrimethylsiloxysilicate type, such as those marketed under the namesX22-4914, X21-5034 and X21-5037 by the company SHIN-ETSU.

The organomodified silicones usable according to the disclosure includebut are not limited to silicones as defined previously, having in theirstructure at least one organofunctional group fixed by a hydrocarbongroup.

In addition to the silicones described above, the organomodifiedsilicones can be polydiaryl siloxanes, such as polydiphenylsiloxanes,and polyalkyl-arylsiloxanes functionalized by the aforementionedorganofunctional groups.

The polyalkarylsiloxanes are, for example, chosen from thepolydimethyl/methylphenylsiloxanes, the polydimethyl/diphenylsiloxanes,linear and/or branched, with viscosity ranging from 1×10⁻⁵ to 5×10² m²/sat 25° C.

Among these polyalkarylsiloxanes, non-limiting mentins can be made ofthe products marketed under the following names: the SILBIONE® oils ofseries 70 641 from RHODIA; the oils of the series RHODORSIL® 70 633 and763 from RHODIA; the oil DOW CORNING® 556 COSMETIC GRADE FLUID from DOWCORNING; the silicones of the PK series from BAYER such as the productPK20; the silicones of the series PN, PH from BAYER such as the productsPN1000 and PH1000; certain oils of the SF series from GENERAL ELECTRICsuch as SF 1023, SF 1154, SF 1250, SF 1265.

Among the organomodified silicones, non-limiting mention can be made ofthe polyorganosiloxanes having: polyoxyethylene and/or polyoxypropylenegroups optionally with C₆-C₂₄ alkyl groups such as the products calleddimethicone copolyol marketed by the company DOW CORNING under the nameDC 1248 or the oils SILWET® L 722, L 7500, L 77, L 711 from the companyUNION CARBIDE and the alkyl(C₁₂)-methicone copolyol marketed by thecompany DOW CORNING under the name Q2 5200; substituted or unsubstitutedamine groups such as the products marketed under the name GP 4 SiliconeFluid and GP 7100 by the company GENESEE or the products marketed underthe names Q2 8220 and DOW CORNING® 929 or 939 by the company DOWCORNING. The substituted amine groups are, for example, C₁-C₄ aminoalkylgroups; alkoxylated groups, such as the product marketed under the name“SILICONE COPOLYMER F-755” by SWS SILICONES and ABIL WAX® 2428, 2434 and2440 by the company GOLDSCHMIDT.

In some embodiments, the at least one fatty substance is neitheralkoxylated, nor glycerolated.

For example, the at least one fatty substance is chosen from compoundsthat are liquid or pasty at room temperature and at atmosphericpressure.

For further example, the at least one fatty substance is a compound thatis liquid at a temperature of 25° C. and at atmospheric pressure.

The at least one fatty substance is, for example, chosen from the loweralkanes, fatty alcohols, esters of fatty acid, esters of fatty alcohol,and oils such as non-silicone mineral, vegetable and synthetic oils, thesilicones.

According to at least one embodiment, the at least one fatty substanceis chosen from liquid paraffin, polydecenes, liquid esters of fattyacids and of fatty alcohols, and mixtures thereof, for example, the atleast one fatty substance of the composition according to the disclosurecan be non-silicone.

In some embodiments, the at least one fatty substance is chosen fromalkanes, hydrocarbons and silicones.

The composition according to the disclosure comprises at least one fattysubstance other than a fatty acid, which is present in the compositionin an amount of at least 10% by weight relative to the total weight ofthe composition. For example, the concentration of fatty substances isfrom about 10% to about 80% by weight, such as from about 15% to about65% by weight, further such as from about 20% to about 55% by weight,based on the total weight of the composition.

Salts

The at least one salt of the present invention may be chosen from alkaliearth metal salts and metal salts.

Suitable alkali earth metal salts may be chosen from Lithium, Sodium,Potassium, Magnesium, Calcium, Barium salts.

Suitable metal salts may be chosen from Manganese, Iron, Copper, Silver,Zinc, Aluminum salts.

In some embodiments, the salt is a mono- or a divalent metal. In someembodiments, the metal salt is a salt of a transition metal. In otherembodiments, the metal salt is not a salt of an alkali earth metal.

The at least one salt of the present invention may be also chosen fromsalt compounds having organic counterions and salt compounds havingpolyatomic counterions such as an ammonium ion or such as a substitutedammonium ion.

In other embodiments, the at least one salt of the present invention maybe chosen from silicates. Suitable silicates include, but are notlimited to, metal silicates, organic silicates and polyatomic silicates.

Within the meaning of the present disclosure, “salt” is understood toinclude, but not limited to, the oxides and hydroxides of metals and thesalts proper that can result from the action of an acid on a metal. Insome embodiments, the at least one salt is not an oxide. In someembodiments, the at least one salt is not a hydroxide. Mention may bemade, among the salts, of halides, such as chlorides, fluorides andiodides, sulfates, phosphates, lactates, acetates, glycinates,aspartates, nitrates, perchlorates, carbonates, hydrogen carbonates,silicates, borates and salts of carboxylic acids and polymeric complexeswhich can support said salts, and also their mixtures.

The salts of carboxylic acids which can be used in the disclosure alsoinclude salts of hydroxylated carboxylic acids, such as gluconate.

Mention may be made, as example of polymeric complexes which can supportsaid salts, of manganese pyrrolidonecarboxylate.

One particularly preferred salt of the present invention is sodiumsulfate.

It was surprisingly found that when the at least one salt is employed inthe compositions of the present invention, less amounts of the alkalineagent and/or the oxidizing agent are necessary in order to achieve thedesired degree of coloring of keratinous substrates. This would be moredesirable since higher levels of the alkaline agent and/or oxidizingagent could result in more damage to the hair.

Moreover, when both the at least one salt and an oxidizing agent arepresent in the compositions of the present invention, peroxy compoundssuch as peroxyacids and peroxysalts, for example, peroxyborates,peroxycarbonates and peroxysulfates, may form in said compositions.

The at least one salt of the present invention can be present in anamount ranging from about 0.001% to about 40% by weight or from about0.05% to about 30% by weight, or from about 0.1% to about 20%, or fromabout 1% to about 15%, based on the total weight of the composition.

Cationic Polymers

In at least one embodiment, the at least one cationic polymer includedin the composition of the disclosure is not chosen from cationicassociative polymers. In other words, these cationic polymers do notcomprise in their structure a pendent or terminal hydrophobic chain, forexample of alkyl or alkenyl type, containing from 10 to 30 carbon atoms.

The at least one cationic polymer of the composition according to thedisclosure can be chosen from, for example:

(1) homopolymers and copolymers derived from acrylic or methacrylicesters or amides and comprising at least one unit chosen from units offormulae (XVI), (XVII), (XVIII) and (XIX):

wherein:

R₃, which may be identical or different, denotes a hydrogen atom or aCH₃ radical;

A, which may be identical or different, represents a linear or branchedC₁-C₆ and, for example, C₂-C₃ alkyl group or a C₁-C₄ hydroxyalkyl group;

R₄, R₅ and R₆, which may be identical or different, represent a C₁-C₁₈alkyl group or a benzyl radical, such as a C₁-C₆ alkyl group;

R₁ and R₂, which may be identical or different, represent hydrogen or aC₁-C₆ alkyl group, for example methyl or ethyl;

X⁻ denotes an anion derived from a mineral or organic acid, such as amethosulfate anion or a halide such as chloride or bromide.

The polymers of this family can also contain at least one unit derivedfrom at least one comonomer which may be chosen from the family ofacrylamides, methacrylamides, diacetone acrylamides, acrylamides andmethacrylamides substituted on the nitrogen with lower (C₁-C₄)alkyls,acrylic or methacrylic acids or esters thereof, vinyllactams such asvinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among the polymers of this family, exemplary mention may be madeof:

copolymers of acrylamide and of dimethylaminoethyl methacrylatequaternized with dimethyl sulfate or with a dimethyl halide, such as theproduct sold under the name HERCOFLOC by the company Hercules,

the copolymers of acrylamide and ofmethacryloyloxyethyltrimethylammonium chloride described, for example,in EP 80 976 and sold under the name BINA QUAT P 100 by the company CibaGeigy,

the copolymer of acrylamide and of methacryloyloxyethyltrimethylammoniummethosulfate sold under the name RETEN by the company Hercules,

quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkylacrylate or methacrylate copolymers, such as the products sold under thename GAFQUAT by the company ISP, for instance GAFQUAT 734 or GAFQUAT755, or alternatively the products known as COPOLYMER 845, 958 and 937,

dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidoneterpolymers, such as the product sold under the name GAFFIX VC 713 bythe company ISP,

vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers sold, forexample, under the name STYLEZE CC 10 by ISP,

quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamidecopolymers such as the product sold under the name GAFQUAT HS100 by thecompany ISP, and crosslinked polymers ofmethacryloyloxy(C₁-C₄)alkyltri(C₁-C₄)alkylammonium salts such as thepolymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized with methyl chloride, or by copolymerization ofacrylamide with dimethylaminoethyl methacrylate quaternized with methylchloride, the homo- or copolymerization being followed by crosslinkingwith a compound containing olefinic unsaturation, such asmethylenebisacrylamide. In at least one embodiment, a crosslinkedacrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer(20/80 by weight) in the form of a dispersion containing 50% by weightof the copolymer in mineral oil can be used. This dispersion is soldunder the name SALCARE® SC 92 by the company Ciba. In some embodiments,a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymercontaining about 50% by weight of the homopolymer in mineral oil or in aliquid ester can be used. These dispersions are sold under the namesSALCARE® SC 95 and SALCARE® SC 96 by the company Ciba.

Other examples are cellulose ether derivatives comprising quaternaryammonium groups, such as the polymers sold under the names JR (JR 400,JR 125, JR 30M) or LR (LR 400, LR 30M) by the company Union CarbideCorporation.

(2) copolymers of cellulose or cellulose derivatives grafted with awater-soluble quaternary ammonium monomer, such as hydroxymethyl-,hydroxyethyl- or hydroxy-propylcelluloses grafted, for instance, with amethacryloylethyltrimethylammonium,methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.These are sold under the name CELQUAT L 200 and CELQUAT H 100 by thecompany National Starch.

(3) non-cellulose cationic polysaccharides, such as guar gums containingtrialkylammonium cationic groups. Such products are sold, for example,under the trade names JAGUAR C13S, JAGUAR C15, JAGUAR C17 and JAGUARC162 by the company Meyhall.

(4) polymers of piperazinyl units and of divalent alkylene orhydroxyalkylene radicals.

(5) water-soluble polyamino amides prepared, for example, bypolycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, adianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, abis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkylhalide or alternatively with an oligomer resulting from the reaction ofa difunctional compound which is reactive with a bis-halohydrin, abis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, anepihalohydrin, a diepoxide or a bis-unsaturated derivative; thecrosslinking agent being used in an amount ranging from 0.025 to 0.35mol per amine group of the polyamino amide; these polyamino amides canbe alkylated or, if they contain at least one tertiary amine function,they can be quaternized. Exemplary mention may be made of the adipicacid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold underthe name CARTARETINE F, F4 or F8 by the company Sandoz.

(6) the polymers obtained by reaction of at least one polyalkylenepolyamine containing two primary amine groups and at least one secondaryamine group with a dicarboxylic acid chosen from diglycolic acid andsaturated C₃-C₈ aliphatic dicarboxylic acids. The molar ratio betweenthe polyalkylene polyamine and the dicarboxylic acid ranges from 0.8:1to 1.4:1; the polyamino amide resulting therefrom is reacted withepichlorohydrin in a molar ratio of epichlorohydrin relative to thesecondary amine group of the polyamino amide ranging from 0.5:1 to1.8:1. Polymers of this type are sold, for example, under the nameHERCOSETT 57, PD 170 or DELSETTE 101 by the company Hercules.

(7) cyclopolymers of alkyldiallylamine and of dialkyldiallylammonium,such as the homopolymers or copolymers containing, as main constituentof the chain, at least one unit corresponding to formula (XX) or (XXI):

wherein formulae k and t are equal to 0 or 1, the sum k+t being equal to1; R₉ denotes a hydrogen atom or a methyl radical; R₇ and R₈,independently of each other, denote a C₁-C₈ alkyl group, a hydroxyalkylgroup in which the alkyl group is C₁-C₅, an amidoalkyl group in whichthe alkyl is C₁-C₄; or R₇ and R₈ denote, together with the nitrogen atomto which they are attached, a heterocyclic group such as piperidyl ormorpholinyl; in at least one embodiment R₇ and R₈, independently of eachother, denote a C₁-C₄ alkyl group; Y— is an organic or mineral anionsuch as bromide, chloride, acetate, borate, citrate, tartrate,bisulfate, bisulfite, sulfate or phosphate.

Among the polymers defined above, exemplary mention may be made of thedimethyldiallylammonium chloride homopolymer sold under the name MERQUAT100 and MERQUAT 280 by the company Nalco (and its homologues of lowweight-average molecular mass) and the copolymers ofdiallyldimethylammonium chloride and of acrylamide, sold under the nameMERQUAT 550.

(8) quaternary diammonium polymers containing repeating units of formula(XXII):

wherein:

R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different, representC₁-C₆ aliphatic, alicyclic or arylaliphatic radicals orhydroxyalkylaliphatic radicals wherein the alkyl radical is C₁-C₄, oralternatively R₁₀, R₁₁, R₁₂ and R₁₃, together or separately, constitute,with the nitrogen atoms to which they are attached, heterocyclesoptionally containing a second heteroatom other than nitrogen, oralternatively R₁₀, R₁₁, R₁₂ and R₁₃ represent a linear or branched C₁-C₆alkyl radical substituted with a nitrile, ester, acyl or amide group ora group—CO—O—R₁₄-D or —CO—NH—R₁₄-D wherein R₁₄ is an alkylene and D is aquaternary ammonium group;

A₁ and B₁ represent C₂-C₆ polymethylene groups which are linear orbranched, saturated or unsaturated, and which optionally contain, linkedto or intercalated in the main chain, at least one aromatic ring or atleast one atom chosen from oxygen and sulfur atom or at least one groupchosen from sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl,quaternary ammonium, ureido, amide and ester groups, and

X⁻ denotes an anion derived from a mineral or organic acid;

A₁, R₁₀ and R₁₂ can form, with the two nitrogen atoms to which they areattached, a piperazine ring;

and wherein, if A₁ denotes a linear or branched, saturated orunsaturated alkylene or hydroxyalkylene radical, B₁ can also denote agroup—(CH₂)_(n)—CO-D-OC—(CH₂)_(n)— wherein n is a number ranging from 1to 6, and D is chosen from:

-   -   a) a glycol residue of formula: —O—Z—O—, where Z denotes a        linear or branched hydrocarbon-based radical or a group        corresponding to one of the following formulae:        —(CH₂—CH₂—O)—CH₂—CH₂—; or —[CH₂—CH(CH₃)—O]_(y)—CH₂—CH(CH₃)—,        where x and y denote an integer ranging from 1 to 4,        representing a defined and unique degree of polymerization or        any number ranging from 1 to 4 representing an average degree of        polymerization;    -   b) a bis-secondary diamine residue such as a piperazine        derivative;    -   c) a bis-primary diamine residue of formula: —NH—Y—NH—, wherein        Y denotes a linear or branched hydrocarbon-based radical, or        alternatively the radical —CH₂—CH₂—S—SCH—CH₂—; and    -   d) an ureylene group of formula: —NH—CO—NH—.

In at least one embodiment, X⁻ is an anion such as chloride or bromide.

These polymers, for example, have a number-average molecular massranging from 1000 to 100,000.

In some embodiments, polymers are used that consist of repeating unitscorresponding to formula (XXIII):

wherein R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different,denote a C₁-C₄ alkyl or hydroxyalkyl radical, n and p are integersranging from 2 to 6, and X⁻ is an anion derived from a mineral ororganic acid.

In at least one embodiment, the at least one cationic polymercorresponding to this family comprise repeating units of formulae (W)and (U):

for example those whose molecular weight, determined by gel permeationchromatography, ranges from 9,500 to 9,900;

for instance those whose molecular weight, determined by gel permeationchromatography, is 1200.

(9) polyquaternary ammonium polymers consisting of repeating units offormula (XXIV):

wherein p denotes an integer ranging from 1 to 6, D may be zero or mayrepresent a group —(CH₂)_(r)—CO— wherein r denotes a number ranging from1 to 6, and X⁻ is an anion.

Such polymers may be prepared according to the processes described inU.S. Pat. Nos. 4,157,388, 4,702,906 and 4,719,282. They are described,for example, in patent application EP 122 324.

Among these polymers, examples that may be mentioned include theproducts MIRAPOL A 15, MIRAPOL AD1, MIRAPOL AZ1 and MIRAPOL 175 sold bythe company Miranol.

(10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, forinstance the products sold under the names LUVIQUAT FC 905, FC 550 andFC 370 by the company BASF.

(11) vinylamide homopolymers or copolymers, such as partially hydrolysedvinylamide homopolymers such as poly(vinylamine/vinylamide)s.

(12) cationic polyurethane derivatives, for example those of elasticnature formed from the reaction:

(a1) of at least one cationic unit resulting from at least one tertiaryor quaternary amine bearing at least two reactive functions containinglabile hydrogen,

(a2) of at least one mixture of at least two different nonionic unitsbearing at least two reactive functions containing labile hydrogen, forinstance chosen from hydroxyl groups, primary or secondary amine groups,and thiol groups, and

(b) of at least one compound comprising at least two isocyanatefunctions.

(13) Other cationic polymers that may be used in the context of thedisclosure include, for example, cationic proteins or cationic proteinhydrolysates, polyalkyleneimines, such as polyethyleneimines, polymerscontaining vinylpyridine or vinylpyridinium units, and chitinderivatives.

Particularly useful cationic polymers in the present invention include,but are not limited to, polyquaternium 4, polyquaternium 6,polyquaternium 7, polyquaternium 10, polyquaternium 11, polyquaternium16, polyquaternium 22, polyquaternium 28, polyquaternium 32,polyquaternium-46, polyquaternium-51, polyquaternium-52,polyquaternium-53, polyquaternium-54, polyquaternium-55,polyquaternium-56, polyquaternium-57, polyquaternium-58,polyquaternium-59, polyquaternium-60, polyquaternium-63,polyquaternium-64, polyquaternium-65, polyquaternium-66,polyquaternium-67, polyquaternium-70, polyquaternium-73,polyquaternium-74, polyquaternium-75, polyquaternium-76,polyquaternium-77, polyquaternium-78, polyquaternium-79,polyquaternium-80, polyquaternium-81, polyquaternium-82,polyquaternium-84, polyquaternium-85, polyquaternium-86,polyquaternium-87, polyquaternium-90, polyquaternium-91,polyquaternium-92, polyquaternium-94, and guar hydroxypropyltrimoniumchloride.

Particularly preferred cationic polymers of the present inventioninclude POLYMER JR-125, POLYMER JR-400, Polymer JR-30M hydroxyethylcellulosic polymers (polyquaternium 10) available from AMERCHOL; JAGUARC® 13-S, guar hydroxypropyltrimonium chloride, available from Rhodia;and MERQUAT® 100 and 280, a dimethyl dialkyl ammonium chloride(polyquaternium 6) available from Nalco.

The cationic polymer is generally present in an amount of from greaterthan 0% to about 15%, preferably from about 0.5% to about 10% by weight,and more preferably from about 1% to about 5% by weight, based on thetotal weight of the composition.

Oxidizing Agent

The compositions of the present disclosure may require an oxidizingagent when the colorant comprises an oxidative dye. Oxidizing agents areused in an amount sufficient for the oxidative dye to develop a color.The oxidizing agents may be, for example, peroxide, a persulfate, aperborate, a percarbonate, alkali metal bromates, ferricyanides or amixture thereof. Oxidizing agents that may also be used include at leastone redox enzyme such as laccases, peroxidases, and 2-electronoxidoreductases, such as uricase, where appropriate in the presence oftheir respective donor or co-factor.

In one embodiment, the oxidizing agent is hydrogen peroxide present inan aqueous solution whose titre may range from 1 to 40 volumes, such asfrom 5 to 40 volumes.

In another embodiment, the oxidizing agent is a persulfate and/or amonopersulfate such as, for example, potassium persulfate, sodiumpersulfate, ammonium persulfate, as well as mixtures thereof. In oneembodiment the oxidizing agents in the present disclosure are selectedfrom hydrogen peroxide, potassium persulfate, sodium persulfate andmixtures thereof.

Typically, the oxidizing agent is provided in the form of a developercomposition.

In one embodiment, the oxidizing agent is present in an amount of atleast 1% by weight, based on the total weight of the developercomposition.

In another embodiment, the oxidizing agent is present in an amountranging from greater than 0% by weight to about 40% by weight, or fromabout 0.01% by weight to about 30% by weight, or from about 0.1% byweight to about % by weight, or from about 1% to about 15% by weight,based on the total weight of the developer composition.

Developer Composition

The developer composition may be in the form of a powder, gel, liquid,foam, lotion, cream, mousse, and emulsion.

In one particular embodiment, the developer composition is aqueous or isin the form of an emulsion.

In another embodiment, the developer composition is substantiallyanhydrous. The term “substantially anhydrous” means that the developercomposition is either completely free of water or contains noappreciable amount of water, for example, no more than 5% by weight, orno more than 2% by weight, or no more than 1% by weight, based on theweight of the developer composition. It should be noted that this refersfor example to bound water, such as the water of crystallization of thesalts or traces of water absorbed by the raw materials used in thepreparation of the compositions according to the disclosure.

The developer composition can contain at least one solvent, chosen fromwater, organic solvents, and mixtures thereof.

When the developer composition is substantially anhydrous, the developercomposition may comprise at least one solvent chosen from organicsolvents.

Suitable organic solvents for use in the developer composition includeethanol, isopropyl alcohol, benzyl alcohol, phenyl ethyl alcohol,glycols and glycol ethers, such as propylene glycol, hexylene glycol,ethylene glycol monomethyl, monoethyl or monobutyl ether, propyleneglycol and its ethers, such as propylene glycol monomethyl ether,butylene glycol, dipropylene glycol, diethylene glycol alkyl ethers,such as diethylene glycol monoethyl ether and monobutyl ether,hydrocarbons such as straight chain hydrocarbons, mineral oil,polybutene, hydrogenated polyisobutene, hydrogenated polydecene,polydecene, squalane, petrolatum, isoparaffins, and mixtures, thereof.

The at least one solvent may, for example, be present in an amountranging from about 0.5% to about 70% by weight, such as from about 2% toabout 60% by weight, preferably from about 5% to about 50% by weight,relative to the total weight of the developer composition.

The pH of the developer composition can range from 2 to 12, such as from6 to 11, and it may be adjusted to the desired value usingacidifying/alkalizing agents that are well known in the art.

Cosmetically Acceptable Medium

The ready-to-use composition according to the disclosure can be invarious forms, such as in the form of liquids, creams, gels, lotions orpaste.

The ready-to-use composition can comprise other compounds constitutingthe cosmetically acceptable medium. This cosmetically acceptable mediumcomprises water or a mixture of water and at least one cosmeticallyacceptable organic solvent.

As examples of organic solvents, non-limiting mentions can be made ofalcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, andphenylethyl alcohol, or glycols or glycol ethers such as, for example,monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propyleneglycol or ethers thereof such as, for example, monomethyl ether ofpropylene glycol, butylene glycol, hexylene glycol, dipropylene glycolas well as alkyl ethers of diethylene glycol, for example monoethylether or monobutyl ether of diethylene glycol.

Additive

The ready-to-use composition according to the disclosure can alsocomprise at least one additive used conventionally in compositions forapplication onto hair.

“Additive” means a substance that is added, different from the compoundsalready mentioned.

As examples of additives that can be used, non-limiting mentions can bemade of surfactants, antioxidants or reducing agents, penetratingagents, sequestering agents, perfumes, buffers, dispersants,conditioners, such as for example volatile or non-volatile, modified orunmodified silicones, film-forming agents, ceramides, preservatives,opacifiers, and antistatic agents.

Preparation and Application of the Ready-to-Use Composition

According one embodiment of the invention, the ready-to-use compositionsaccording to the disclosure can be prepared from a dye compositioncomprising at least one direct dye as defined previously, with orwithout any developer composition.

According to another embodiment of the invention the ready-to-usecompositions according to the disclosure can result from mixing twounits, including a first unit of an oxidative dye containing compositionas defined previously and a second unit of a developer composition asdefined above, or vice versa.

According to yet another embodiment of the invention, a pre-treatmentcomposition containing at least one salt may be provided and appliedonto the keratinous substrates prior to the application of theready-to-use composition.

It has been surprisingly discovered that the composition of the presentinvention enables acceptable levels of dye to be deposited ontokeratinous substrates utilizing lower amounts of dye compared toconventional dyeing compositions.

Yet another surprising discovery is that in the event conventionalamounts of dye are employed, the dyeing process may be completed in lesstime such as 20 minutes or 15 minutes or 10 minutes, thereby causingless damage to the keratinous substrates.

In the event that conventional levels of dye are employed, coupled withconventional dyeing times, significantly larger color deposit onto thekeratinous substrate may be achieved.

Finally, the inventive composition contains large amounts of water,e.g., higher than 60%, or 80% by weight, which advantageously lowers thecost of production.

According to another embodiment of the invention, a kit for dyeingkeratinous substrates is provided, comprising:

a first unit containing in a cosmetically acceptable medium: at leastone fatty quaternary amine compound; at least one nonionic surfactant;at least one phosphate ester chosen from alkoxylated alkyl phosphateesters and alkyl phosphate esters; and at least one dye chosen fromoxidation dye precursors and direct dyes; optionally, at least onethickening agent; optionally, at least one alkaline agent; optionally,at least one fatty substance other than a fatty acid; and optionally, atleast one salt; and

a second unit comprising at least one oxidizing agent and optionally, atleast one fatty substance other than a fatty acid.

According to yet another embodiment of the invention, the kit furthercomprises a third unit containing at least one salt in a cosmeticallyacceptable medium.

The present invention will be better understood by the examples whichfollow, all of which are intended for illustrative purposes only, andare not meant to unduly limit the scope of the invention in any way.

EXAMPLES

The following example is intended for illustrative purposes only, and isnot meant to unduly limit the scope of the invention in any way.

Example 1

(Low pH Blue Binary Color Deposit Study)

A test swatch of IHIP 90% gray hair (1 cm width, 15 cm length) was dyedwith 20 g of the mixture of the below dye composition mixed 1:1 withL'Oreal Majicreme™ 20 volume developer. The pH of the final mixture wasadjusted to 6.5 using NaOH.

Ingredients Example 1 DI Water Q.S. Behentrimonium Chloride 2.0% PPG-5Ceteth-20 16.0% Dimethicone PEG-7 Phosphate 6.0% Mineral Oil 1.0%N,N-Bis (2-hydroxyethyl) p- 1.47% phenylenediamine Sulfate2,4-Diaminophenoxyethanol HCl 1.205%

A control swatch was dyed with the mixture of Redken Shades EQ™ clear,containing the same dyes at same levels as above, mixed 1:1 with RedkenShades EQ™ Processing solution. The pH of the final mixture was adjustedto 6.5 using NaOH.

Both swatches were processed for 20 minutes at RT, rinsed for 1 minute(80 gph, 32° C.), and dried. L*a*b* values were measured before andafter coloring using Konica Minolta Spectrophotometer.

The final ΔL value measurements for the control and test swatches were−54.32 and −65.02, respectively. More negative ΔL value indicates darkercolor. The color intensity difference is also visually significant.Therefore the inventive formula deposits greater amounts of color on thehair than the control in the 20 minutes processes.

Example 2

(High pH Blue Binary Color Deposit Study)

A test swatch of IHIP 90% gray hair (1 cm width, 15 cm length) was dyedwith 20 g of the mixture of the below dye composition mixed 1:1 withL'Oreal Majicreme™ 20 volume developer. The pH of the final mixture wasadjusted to 9.5 using NaOH.

Ingredients Example 2 DI Water Q.S. Behentrimonium Chloride 2.0% PPG-5Ceteth-20 16.0% Dimethicone PEG-7 Phosphate 6.0% Mineral Oil 1.0%N,N-Bis (2-hydroxyethyl) p- 1.47% phenylenediamine Sulfate2,4-Diaminophenoxyethanol HCl 1.205%

A control swatch was dyed with the mixture of L'Oreal Preference™ basecontaining the same dyes at same levels as above, mixed 1:1 with L'OrealPreference™ 20 volume developer. The pH of the final mixture wasadjusted to 9.5 using NaOH.

Both swatches were processed for 20 minutes at RT, rinsed for 1 minute(80 gph, 32° C.), and dried. L*a*b* values were measured before andafter coloring using Konica Minolta Spectrophotometer.

The final ΔL value measurements for the control and test swatches were−54.32 and −67.78, respectively. More negative ΔL value indicates darkercolor. The color intensity difference is also visually significant.Therefore the inventive formula deposits greater amounts of color on thehair than the control in the 20 minutes processes.

Example 3

(Wet Combing Study)

Six untreated IHIP regular bleached hair swatches (1 inch width, 5.5inch length) were measured for Energy Break (the energy needed to combthrough the whole hair swatch), using the Instron wet combing machine.The swatches were then dyed with 15 g of the mixture of the below dyecomposition mixed 1:1 with L'Oreal Preference™ 20 volume developer.

Ingredients Example 3 DI Water Q.S. Behentrimonium Chloride 2.0% PPG-5Ceteth-20 16.0% Dimethicone PEG-7 Phosphate 6.0% Mineral Oil 1.0%1-Hydroxyethyl 4,5 Diamino 1.201% pyrazole sulfate 5-amino-o-cresol0.615%

The dyed swatches were measured wet for final Energy Break reading. Theaverage Energy break readings of the untreated and the dyed swatcheswere 594.87 and 91.08 g-in, respectively. These values are statisticallysignificant. The average percent change in combing is −83.43, thereforethe hair is about 83% smoother than before coloring. Thus, the inventiveformula is providing better conditioning to the hair.

It will be apparent to those skilled in the art that numerousmodifications and variations can be made without departing from thespirit or scope of the invention.

What is claimed is:
 1. A ready-to-use aqueous composition for dyeingkeratinous substrates comprising, in a cosmetically acceptable medium:a) at least one fatty quaternary amine compound; b) at least onenonionic surfactant; c) at least one anionic silicone; d) at least onedye chosen from oxidation dye precursors and direct dyes; e) optionally,at least one thickening agent; f) optionally, at least one alkalineagent; g) optionally, at least one fatty substance other than a fattyacid; h) optionally, at least one salt; and i) at least one oxidizingagent.
 2. The composition of claim 1 wherein (a) is behentrimoniumchloride.
 3. The composition of claim 1 wherein (a) is present in anamount of from greater than 0 to about 30% by weight, based on theweight of the composition.
 4. The composition of claim 1 wherein (a) ispresent in an amount of from about 1 to about 10% by weight, based onthe weight of the composition.
 5. The composition of claim 1 wherein (b)has an HLB of at least about
 8. 6. The composition of claim 1 wherein(b) is present in an amount of from greater than 0 to about 70% byweight, based on the weight of the composition.
 7. The composition ofclaim 1 wherein (b) is present in an amount of from about 1 to about 30%by weight, based on the weight of the composition.
 8. The composition ofclaim 1 wherein (c) is a silicone phosphate.
 9. The composition of claim1 wherein (c) is a silicone carboxylate.
 10. The composition of claim 1wherein (c) is a silicone sulfate.
 11. The composition of claim 1wherein (c) is present in an amount of from greater than 0 to about 40%by weight, based on the weight of the composition.
 12. The compositionof claim 1 wherein (c) is present in an amount of from about 0.5 toabout 20% by weight by weight, based on the weight of the composition.13. The composition of claim 1, wherein (d) is chosen from oxidationbases and couplers, and mixtures thereof.
 14. The composition of claim1, wherein (d) is chosen from ortho- and para-phenylenediamine oxidationbases, double bases, ortho- and para-aminophenols, heterocyclic bases,as well as salts of addition of these compounds with an acid andmeta-aminophenol, meta-phenylenediamine, meta-diphenol, naphtholcouplers, heterocyclic couplers and acid salts thereof.
 15. Thecomposition of claim 1, wherein (d) is chosen from aminophenols andmeta-phenylenediamines.
 16. The composition of claim 1, wherein (d) ischosen from direct dyes.
 17. The composition of claim 1, wherein (e) ischosen from a polymeric thickener and a non-polymeric thickener and ispresent in an amount of from about 0.01 to about 10% by weight.
 18. Thecomposition of claim 1, wherein (e) is present in an amount of fromabout 0.5 to about 5% by weight.
 19. The composition of claim 1, wherein(f) is chosen from organic amines, organic amine salts, ammonium salts,and inorganic bases and is present from about 0.001% to about 30% byweight.
 20. The composition of claim 1, wherein (f) is present in anamount of from about 0.1 to about 15% by weight.
 21. The composition ofclaim 1, wherein (g) is chosen from lower alkanes, fatty alcohols,esters of fatty acids, esters of fatty alcohol, non-silicone oils,non-silicone waxes and silicones and is present in an amount of fromabout 10 to about 80% by weight.
 22. The composition of claim 1, wherein(g) is non-silicone.
 23. The composition of claim 1, wherein (g) ispresent in an amount of from about 20 to about 55% by weight.
 24. Thecomposition of claim 1, wherein (h) is chosen from salt compounds ofhalides, sulfates, phosphates, lactates, acetates, glycinates,aspartates, nitrates, perchiorates, carbonates, hydrogen carbonates,silicates, borates, and carboxylic acids and is present in an amount offrom about 0.001% to about 40% by weight.
 25. The composition of claim1, wherein (h) is present in an amount of from about 0.1 to about 20% byweight.
 26. The composition of claim 1, wherein (h) is sodium sulfate.27. The composition of claim 1, wherein (i) is chosen from peroxides,bromates of alkali metals, ferricyanides of alkali metals, peroxygenatedsalts, oxidoreduction enzymes, and oxygen in air and is present in anamount of from about 0.001% to about 40% by weight.
 28. The compositionof claim 1, wherein (i) is present in an amount of from about 0.1 toabout 20% by weight.
 29. The composition of claim 1, wherein (i) ishydrogen peroxide.
 30. The composition of claim 1 wherein thecomposition further comprises a cationic polymer and is present in anamount of from greater than 0% to about 15% by weight.
 31. Thecomposition of claim 1 wherein the composition further comprises acationic polymer and is present in an amount of from about 1% to about5% by weight.
 32. The composition of claim 1 is substantially free ofammonia.
 33. The composition of claim 1 wherein the pH of thecomposition is at least
 9. 34. The composition of claim 1 wherein the pHof the composition is from about 9 to about
 11. 35. The composition ofclaim 1 wherein the pH of the composition is less than or equal to 7.36. The composition of claim 1 wherein the pH of the composition is fromabout 6 to about
 7. 37. A method of dyeing keratinous substrates,comprising applying onto the keratinous substrates a ready-to-useaqueous composition containing, in a cosmetically acceptable medium: a)at least one fatty quaternary amine; b) at least one nonionicsurfactant; c) at least one anionic silicone; d) at least one dye chosenfrom oxidation dye precursors and direct dyes; e) optionally, at leastone thickening agent; f) optionally, at least one alkaline agent; g)optionally, at least one fatty substance other than a fatty acid; h)optionally, at least one salt; and i) at least one oxidizing agent. 38.The method of claim 37 further comprising: a) providing a pre-treatmentcomposition containing at least one salt; and b) applying thepre-treatment composition prior to the application of the ready-to-useaqueous composition, wherein the pretreatment composition comprises atleast one salt in a cosmetically acceptable medium.
 39. A ready-to-useaqueous composition for the oxidative dyeing of keratinous substratescomprising, in a cosmetically acceptable medium, a) from about 1 toabout 10% by weight at least one fatty quaternary amine compound; b)from about 1 to about 30% by weight at least one nonionic surfactant; c)from about 0.5 to about 20% by weight at least one anionic silicone; d)at least one oxidative dye chosen from oxidation bases and couplers; e)optionally, at least one thickening agent; f) from about 0.1 to about15% by weight of at least one alkaline agent; g) at least 10% by weightof at least one fatty substance other than a fatty acid; h) optionally,at least one salt; and i) from about 0.1 to about 20% by weight of atleast one oxidizing agent.
 40. A kit for dyeing keratinous substrates,comprising: 1) a first unit containing, in a cosmetically acceptablemedium: a) at least one fatty quaternary amine compound; b) at least onenonionic surfactant; c) at least one anionic silicone; d) at least oneoxidative dye chosen from oxidation bases and couplers; and e)optionally, at least one thickening agent; f) optionally, at least onealkaline agent; g) optionally, at least one fatty substance other than afatty acid; and h) optionally, at least one salt; and 2) a second unitcomprising at least one oxidizing agent and optionally, at least onefatty substance other than a fatty acid.
 41. A kit for dyeing keratinoussubstrates, comprising: 1) a first unit containing, in a cosmeticallyacceptable medium: a) at least one fatty quaternary amine compound; b)at least one nonionic surfactant; c) at least one anionic silicone; d)at least one oxidative dye chosen from oxidation bases and couplers; ande) optionally, at least one thickening agent; f) optionally, at leastone alkaline agent; g) optionally, at least one fatty substance otherthan a fatty acid; and h) optionally, at least one salt; 2) a secondunit comprising at least one oxidizing agent and optionally, at leastone fatty substance other than a fatty acid and 3) a third unitcomprising at least one salt in a cosmetically acceptable medium.